Abrasion-resistant thermoformable coating and preparation of same

ABSTRACT

Coating compositions including a nanoparticle layer including nanoparticles and a curable resin and a curable resin layer comprising the curable resin, where the nanoparticle layer has a thickness of 0.2 μm to 8 μm, and where the nanoparticle layer includes less than 40 vol. % of the curable resin. Methods for preparing the coating compositions, laminates including the coating compositions, and articles including the laminates are provided.

TECHNICAL FIELD The present disclosure generally relates toabrasion-resistant coatings including nanoparticles and methods ofpreparing such coatings. BACKGROUND

A hardcoat can be useful as a protective layer on a substrate,particularly when the substrate may be exposed to physical wear and/orextreme weather conditions. For example, hardcoats have been used toprotect the face of optical displays. Such hardcoats typically containinorganic oxide particles, e.g., silica, of nanometer dimensionsdispersed in a binder precursor resin matrix, and are described, forexample, in U.S. Pat. No. 9,377,563 (Hao et al.).

SUMMARY

In one aspect, provided herein are coating compositions including ananoparticle layer including nanoparticles and a curable resin and acurable resin layer comprising the curable resin, where the nanoparticlelayer has a thickness of 0.2 μm to 8 μm, and where the nanoparticlelayer includes less than 40 vol. % of the curable resin.

In another aspect, provided herein are laminates including the disclosedcoating compositions and articles including such laminates.

In another aspect, provided herein are methods of coating a substratewith the disclosed coating compositions.

As used herein,

The terms “cure” and “curing” refer to processes through which amaterial hardens and/or becomes solid. Curing can include processes suchas, for example, polymerization, crosslinking, drying, cooling frommelt, electrolyte complexation, and combinations thereof.

The term “alkyl” refers to a monovalent group which is a saturatedhydrocarbon. The alkyl can be linear, branched, cyclic, or combinationsthereof and typically has 1 to 30 carbon atoms. In some embodiments, thealkyl group contains 1 to 30, 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6,or 1 to 4 carbon atoms. Examples of alkyl groups include, but are notlimited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and2-ethylhexyl.

The term “(meth)acrylate” refers to an acrylate, a methacrylate, orboth.

The term “aspect ratio” refers to the ratio between the length (i.e.,longest dimension) and the width (i.e., the shortest dimension) or thediameter of a particle.

The term “precursor” refers to a constituent part or reactant which,when reacted, cured, and/or polymerized will form a hardened material. Aprecursor may include a monomer and/or an oligomer.

Features and advantages of the present disclosure will be furtherunderstood upon consideration of the detailed description as well as theappended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of an exemplary article ofthe present disclosure.

FIG. 2 is a schematic representation of a method for preparing anarticle according to some embodiments of the present disclosure.

FIG. 3A is an image of silica nanoparticles dispersed in isopropanol, 10to 15 nm particle size, supplied at 30% solids from Nissan ChemicalAmerica Corporation.

FIG. 3B is an image of silica nanoparticles dispersed in isopropanol, 40to 50 nm particle size, supplied at 30% solids from Nissan ChemicalAmerica Corporation.

FIG. 3C is an image of silica nanoparticles dispersed in isopropanol, 9to 15 nm particle strand diameter and 40 to 100 nm overall length,supplied at 15% solids from Nissan Chemical America Corporation.

FIG. 4 is a scanning electron microscopy (“SEM”) image of across-section of an article according to the present disclosure.

FIG. 5 is an SEM image of a cross-section of the top layer (i.e., thenanoparticle layer) of the article of FIG. 4 .

FIG. 6 is a schematic representation of an apparatus for preparing alaminate article according to some embodiments of the presentdisclosure.

FIG. 7 is a schematic representation of steps for preparing a lensincluding a thermoformed laminate of the present disclosure.

FIG. 8A is a top view of a thermoforming mold useful in some embodimentsof the present disclosure.

FIG. 8B is a section view of the thermoforming mold of FIG. 8A.

Repeated use of reference characters in the specification and drawingsis intended to represent the same or analogous features or elements ofthe disclosure. It should be understood that numerous othermodifications and embodiments can be devised by those skilled in theart, which fall within the scope and spirit of the principles of thedisclosure. The figures may not be drawn to scale.

DETAILED DESCRIPTION

To achieve a desired abrasion resistance effect, hardcoat formulationscan commonly include up to 40 wt. % of a filler, such as, for example,nano-silica particles. However, an abundance of filler particles in thehardcoat bulk may be undesirable in some circumstances. For example,hardcoats including an abundance of filler particles distributedthroughout the hardcoat bulk, particularly when used outdoors, tend tosuffer embrittlement and hazing issues, i.e., weathering, due to theamount of nano-silica present in the hardcoat resin formulations.Furthermore, hardcoats including an abundance of filler particlesdistributed throughout the hardcoat bulk are often unsuitable for use inthermoforming processes due to the rigidity imparted to the coating bythe addition of the nano-silica particles, rigidity which can lead toformation of defects, e.g., cracks, hazing, in the thermoformed product.

By constructing the hardcoat according to the present disclosure, thetotal amount of nano-silica filler required in the formulation can bereduced by forcing the filler to concentrate at the coating surfacewhere it may be most effective at retarding abrasion. It has beensurprisingly discovered that such coatings exhibit superior abrasionresistance when compared to coatings including silica nanoparticlesdispersed throughout the thickness of the coating layer whilemaintaining sufficient flexibility for use in thermoforming processes.This reduced level of nano-silica in the hardcoat may also have apositive impact on the resistance to outdoor weathering of the product.

Provided herein are coating compositions including a nanoparticle layerincluding nanoparticles and a curable resin and a curable resin layercomprising the curable resin, where the nanoparticle layer has athickness of 0.2 μm to 8 μm, and where the nanoparticle layer includesless than 40 vol. % of the curable resin. FIG. 1 shows a cross-sectionalview of an exemplary coating composition 10 prepared according to someembodiments of methods of the present disclosure. As shown in FIG. 1 ,coating composition 10 includes a nanoparticle layer 20 having a firstmajor surface 22 and an opposing second major surface 24 and a curableresin layer 40 having a first major surface 42 and a second opposingmajor surface 44. The nanoparticle layer 20 and the curable resin layer40 are adjacent each other at interface 30.

Provided herein are laminates including the coating composition and asubstrate, where the substrate is adjacent to the curable resin layer.Also provided herein are articles including the laminates.

Nanoparticle Layer

The nanoparticle layer may include particles comprising, for example,silica, alumina, ceria, diamond, titanium dioxide, zinc oxide, tungstenoxide, zirconia, calcium carbonate, magnesium silicate, indium tinoxide, antimony tin oxide, tungsten bronze, and combinations thereof.The nanoparticle layer may be formed by methods known to those ofordinary skill in the art, for example, by applying silica nanoparticlesdispersed in a solvent (e.g., isopropanol) onto a disposable linermaterial (e.g., polypropylene) and allowing the solvent to evaporatefrom the nanoparticle layer.

A variety of materials are suitable for use as the liner material,including both flexible materials and materials that are more rigid. Dueto their ability to facilitate separation of the coating compositionfrom the liner material, flexible materials may be preferred. The linermay include, for example, a polymeric film, a primed polymeric film, ametal foil, a cloth (e.g., a textile), a paper, a vulcanized fiber, anonwoven material and treated versions thereof, and combinationsthereof. In some embodiments, the liner is non-porous. In someembodiments the liner may include, for example, a material selected fromthe group consisting of a silicon, a glass, a metal, a metal oxide, apolymeric film, and combinations thereof. In some embodiments, forexample, where the curable resin is designed to be polymerized, i.e.,cured, by actinic radiation, or when greater flexibility is desired, theliner may be a polymeric film or treated polymeric film. Examples ofsuch films include, but are not limited to, polyester film (e.g.,polyethylene terephthalate film, polybutylene terephthalate film,polybutylene succinate film, polylactic acid film), co-polyester film,polyimide film, polyamide film, polyurethane film, polycarbonate film,polyvinyl chloride film, polyvinyl alcohol film, polypropylene film(e.g., biaxially oriented polypropylene), polyethylene film, poly(methylmethacrylate) film, and the like. In some embodiments, the film layermay be biodegradable film, e.g. polybutylene succinate film, polylacticacid film. In some embodiments laminates of different polymer films maybe used to form the liner. In embodiments wherein curable resin isdesigned to be polymerized, i.e. cured, by actinic radiation, thedisposable liner may allow for sufficient transmission of the actinicradiation to enable polymerization. In some embodiments, the liner has apercent transmission of at least 50 percent, at least 60 percent, atleast 70 percent, at least 80 percent, at least 90 percent or at least95 percent over at least a portion of the UV/Visible light spectrum. Insome embodiments, the liner has a percent transmission of at least 50percent, at least 60 percent, at least 70 percent, at least 80 percent,at least 90 percent or at least 95 percent over at least a portion ofthe visible light spectrum (about 400 to 700 nm). The percenttransmission may be measured by conventional techniques and equipment,such as using a HAZEGARD PLUS haze meter from BYK-Gardner Inc., SilverSprings, Maryland, to measure the percent transmission of a film layerhaving an average thickness of from 1 to 100 micrometers. In someembodiments, the thickness of the film layer may be 1 to 1,000micrometers, 1 to 500 micrometers, 1 to 200 micrometers, or 1 to 100micrometers. In some embodiments, the liner may include an antistaticmaterial or the liner may include an antistatic coating on one or bothof its major surfaces.

In some preferred embodiments, the particles of the nanoparticle layermay be of a uniform size and shape such as, for example, a sphericalshape having an average diameter of 1 nm to 100 nm (e.g., 20 nm),optionally 1 nm to 400 nm, optionally 2 nm to 200 nm, or optionally 5 nmto 100 nm. In some embodiments, the particles of the nanoparticle layermay be of an irregular shape, i.e., the particles may have an aspectratio greater than 1:1, e.g., or a mixture of regular and/or irregularshapes. In some preferred embodiments, the nanoparticles may have anaspect ratio of 2:1 to 12:1, optionally 3:1 to 11:1, optionally 4:1 to10:1, or optionally 5:1 to 9:1. In some preferred embodiments, thenanoparticles comprise an elongated silica nanoparticle having adiameter of 9 nm to 15 nm and a length of 40 nm to 100 nm. Examples ofnanoparticles useful in embodiments of the present disclosure are shown,for example, in FIGS. 3A-3C. In some embodiments, the nanoparticles maybe coated with another material, such as, for example, a silane coatingas described in U.S. Pat. Pub. 2015/0017386 A1 (Kolb et al.).

The nanoparticle layer commonly has a thickness of thickness of 0.2 μmto 8 μm, optionally 0.4 μm to 6 μm, optionally 0.8 μm to 4 μm, oroptionally 1 μm to 3 μm and comprises less than 40 vol. %, less than 30vol. %, less than 20 vol. %, less than 10 vol. %, less than 5 vol. %, orless than 1 vol. % of the curable resin that has interpenetrated thenanoparticle layer from the curable resin layer during formation of thecoating composition. Though not wishing to be bound by a particulartheory, it is believed that the curable resin may be drawn throughinterstices of the nanoparticle layer structure into the thickness ofthe nanoparticle layer by a process such as, for example, capillaryaction when the nanoparticle layer is contacted with the curable resinduring formation of the coating composition. In preferred embodiments,the opposing major surfaces of the nanoparticle layer are planar andflat, i.e., the major surfaces do not generally include structures(e.g., nanostructures) extending from or carved into the major surfaces.

Curable Resin

The composition of the curable resin is not particularly limited. Thecurable resin is capable of being cured and the curing technique is notparticularly limited and may include, for example, curing by actinicradiation, thermal curing, e-beam curing and combinations thereof.Actinic radiation may include electromagnetic radiation in the UV, e.g.100 to 400 nm, and visible range, e.g. 400 to 700 nm, of theelectromagnetic radiation spectrum. Due to its rapid curecharacteristics, the curing of the curable resin by actinic radiationmay be preferred. The curable resin may include monomers, oligomersand/or polymers that can be cured by conventional free-radicalmechanisms.

In some embodiments, the curable resin includes one or more(meth)acrylates. The (meth)acrylate may be at least one of monomeric,oligomeric and polymeric. The (meth)acrylate may be polar, non-polar ormixtures thereof. Non-polar (meth)acrylate may include alkylmeth(acrylate). Useful non-polar (meth)acrylate include, but are notlimited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl(meth)acrylate, iso-pentyl (meth)acrylate (i.e., iso-amyl(meth)acrylate), 3-pentyl (meth)acrylate, 2-methyl-1-butyl(meth)acrylate, 3-methyl-1-butyl (meth)acrylate, stearyl (meth)acrylate,phenyl (meth)acrylate, n-hexyl (meth)acrylate, iso-hexyl (meth)acrylate,cyclohexyl (meth)acrylate, 2-methyl-1-pentyl (meth)acrylate,3-methyl-1-pentyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate,2-ethyl-1-butyl (meth)acrylate, 2-methy-l-hexyl(meth)acrylate,3,5,5-trimethyl-1-hexyl (meth)acrylate, cyclohexyl (meth)acrylate,3-heptyl (meth)acrylate, benzyl (meth)acrylate, n-octyl (meth)acrylate,iso-octyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethyl-1-hexyl(meth)acrylate, n-decyl (meth)acrylate, iso-decyl (meth)acrylate,isobornyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isononyl(meth)acrylate, isophoryl (meth)acrylate, n-dodecyl (meth)acrylate(i.e., lauryl (meth)acrylate), n-tridecyl (meth)acrylate, iso-tridecyl(meth)acrylate, 3,7-dimethyl-octyl (meth)acrylate, and any combinationsor mixtures thereof. Combinations of non-polar (meth)acrylates may beused.

Polar (meth)acrylates include, but are not limited to, 2-hydroxyethyl(meth)acrylate; poly(alkoxyalkyl) (meth)acrylates including2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,2-methoxyethoxyethyl (meth)acrylate, 2-methoxyethyl methacrylate;alkoxylated (meth)acrylates (e.g. ethoxylated and propoxylated(meth)acrylate), and mixtures thereof. The alkoxylated (meth)acrylatesmay be monofunctional, difunctional, trifunctional or have higherfunctionality. Ethoxylated acrylates include, but are not limited to,ethoxylated (3) trimethylolpropane triacrylate (available under thetrade designation “SR454”, from Sartomer, Exton, Pennsylvania),ethoxylated (6) trimethylolpropane triacrylate (available under thetrade designation “SR499”, from Sartomer), ethoxylated (6)trimethylolpropane triacrylate (available under the trade designation“MIRAMER M3160” from Miwon North America Inc., Exton

Pennsylvania), ethoxylated (9) trimethylolpropane triacrylate (availableunder the trade designation “SR502”, from Sartomer), ethoxylated (15)trimethylolpropane triacrylate (available under the trade designation“SR9035”, from Sartomer), ethoxylated (20) trimethylolpropanetriacrylate (available under the trade designation “SR415”, fromSartomer), polyethylene glycol (600) diacrylate (available under thetrade designation “SR610”, from Sartomer), polyethylene glycol (400)diacrylate (available under the trade designation “SR344”, fromSartomer), polyethylene glycol (200) diacrylate (available under thetrade designation “SR259”, from Sartomer), ethoxylated (3) bisphenol Adiacrylate (available under the trade designation “SR349”, fromSartomer), ethoxylated (4) bisphenol A diacrylate (available under thetrade designation “SR601”, from Sartomer), ethoxylated (10) bisphenol Adiacrylate (available under the trade designation “SR602”, fromSartomer), ethoxylated (30) bisphenol A diacrylate (available under thetrade designation “SR9038”, from Sartomer), propoxylated neopentylglycol diacrylate (available under the trade designation “SR9003”, fromSartomer), polyethylene glycol dimethacrylate (available under the tradedesignation “SR210A”, from Sartomer), polyethylene glycol (600)dimethacrylate (available under the trade designation “SR252”, fromSartomer), polyethylene glycol (400) dimethacrylate (available under thetrade designation “SR603”, from Sartomer), ethoxylated (30) bisphenol Adimethacrylate (available under the trade designation “SR9036”, fromSartomer. Combinations of polar (meth)acrylates may be used.

Other monomers that may be used and considered to be in the category ofpolar (meth)acrylates include N-vinylpyrrolidone; N-vinylcaprolactam;acrylamides; mono- or di-N-alkyl substituted acrylamide; t-butylacrylamide; dimethylaminoethyl acrylamide; N-octyl acrylamide and;acrylic acid, and methacrylic acid, and alkyl vinyl ethers, includingvinyl methyl ether.

In some embodiments, the curable resin includes a precursor, such as,for example a polyurethane precursor, an epoxy precursor (typically anepoxide and hardener), a polyurea precursor, or combinations thereof.

In some embodiments, the curable resin includes a crosslinker. Thecrosslinker often increases the cohesive strength and the tensilestrength of the cured adhesive layer. The crosslinker can have at leasttwo functional groups, e.g., two ethylenically unsaturated groups, whichare capable of polymerizing with other components of the curable resin.Suitable crosslinkers may have multiple (meth)acryloyl groups.Alternatively, the crosslinker can have at least two groups that arecapable of reacting with various functional groups (i.e., functionalgroups that are not ethylenically unsaturated groups) on anothermonomer. For example, the crosslinker can have multiple groups that canreact with functional groups such as acidic groups on other monomers.

Crosslinkers with multiple (meth)acryloyl groups can bedi(meth)acrylates, tri(meth)acrylates, tetra(meth)acrylates,penta(meth)acrylates, and the like. In many aspects, the crosslinkerscontain at least two (meth)acryloyl groups. Exemplary crosslinkers withtwo acryloyl groups include, but are not limited to, 1,2-ethanedioldiacrylate, 1,3-propanediol diacrylate, 1,9-nonanediol diacrylate,1,12-dodecanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanedioldiacrylate, butylene glycol diacrylate, bisphenol A diacrylate,diethylene glycol diacrylate, triethylene glycol diacrylate,tetraethylene glycol diacrylate, tripropylene glycol diacrylate,polyethylene glycol diacrylate, polypropylene glycol diacrylate,polyethylene/polypropylene copolymer diacrylate, polybutadienedi(meth)acrylate, propoxylated glycerin tri(meth)acrylate, andneopentylglycol hydroxypivalate diacrylate modified caprolactone.

Exemplary crosslinkers with three or four (meth)acryloyl groups include,but are not limited to, trimethylolpropane triacrylate (available underthe trade designation “TMPTA-N” from Cytec Industries, Inc., Smyrna, Ga.and under the trade designation “SR351” from Sartomer), pentaerythritoltriacrylate (available under the trade designation “SR444” fromSartomer), tris(2-hydroxyethylisocyanurate) triacrylate (available underthe trade designation “SR368” from Sartomer), a mixture ofpentaerythritol triacrylate and pentaerythritol tetraacrylate (availableunder the trade designation “PETIA” with an approximately 1:1 ratio oftetraacrylate to triacrylate and under the trade designation “PETA-K”with an approximately 3:1 ratio of tetraacrylate to triacrylate, fromCytec Industries, Inc.), pentaerythritol tetraacrylate (available underthe trade designation “SR295” from Sartomer”), di-trimethylolpropanetetraacrylate (available under the trade designation “SR355” fromSartomer), and ethoxylated pentaerythritol tetraacrylate (availableunder the trade designation “SR494” from Sartomer). An exemplarycrosslinker with five (meth)acryloyl groups includes, but is not limitedto, dipentaerythritol pentaacrylate (available under the tradedesignation “SR399” from Sartomer). Previously mentioned multifunctionalpolar (meth)acrylate may be considered crosslinkers.

In some aspects, the crosslinkers are polymeric materials that containat least two (meth)acryloyl groups. For example, the crosslinkers can bepoly(alkylene oxides) with at least two acryloyl groups (polyethyleneglycol diacrylates commercially available from Sartomer under the tradedesignation “SR210”, “SR252”, and “SR603”, for example). Thecrosslinkers poly(urethanes) with at least two (meth)acryloyl groups(polyurethane diacrylates such as CN9018 from Sartomer). As the highermolecular weight of the crosslinkers increases, the resulting acryliccopolymer tends to have a higher elongation before breaking. Polymericcrosslinkers tend to be used in greater weight percent amounts comparedto their non-polymeric counterparts.

Other types of crosslinkers can be used rather than those having atleast two (meth)acryloyl groups. The crosslinker can have multiplegroups that react with functional groups such as acidic groups on othermonomers. For example, monomers with multiple aziridinyl groups can beused that are reactive with carboxyl groups. For example, thecrosslinkers can be a bis-amide crosslinker as described in U.S. Pat.No. 6,777,079 (Zhou et al.).

The amount of crosslinker in the curable resin is not particularlylimited and depends on the desired final properties of the curedadhesive layer formed therefrom. Crosslinking may improve the cohesivestrength of the cured adhesive layer and facilitate removal from thesurface of the substrate without leaving residue while improving theability of the cured adhesive layer to entrap the particulatecontaminant and remove it from the substrate surface. In someembodiments the curable resin may include at least 5 percent, at least10 percent, at least 30 percent, at least 40 percent, at least 50percent, at least 60 percent at least 70 percent, at least 80 percent,at least 90 percent, at least 95 percent or at least 97 percent byweight of crosslinker. In some embodiments the curable resin may includeat least 5 percent at least 10 percent, at least 20 percent, at least 30percent and/or less than 100 percent, less than 99 percent, less than 97percent, less than 95 percent, less than 90 percent, less than 85percent by weight of crosslinker. In some embodiments the curable resinmay include from between 50 and 100 percent, between and 100 percent,between 70 and 100 percent, between 80 and 100 percent, between 90 and100 percent, between 50 and 98 percent, between 60 and 98 percent,between 70 and 98 percent, between 80 and 98 percent, between 90 and 98percent, between 50 and 95 percent, between 60 and 95 percent, between70 and 95 percent, between 80 and 95 percent, between 90 and 95 percentby weight of the crosslinker. In some embodiments, the crosslinker is apolar meth(acrylate).

In some embodiments, the curable resin comprises a (meth)acrylate resin,a polyurethane precursor, an epoxy precursor (epoxide and hardener), apolyurea precursor, a cyanoacrylate resin, a polyester (meth)acrylateresin, a polyurethane (meth)acrylate resin, and combinations thereof. Insome preferred embodiments the curable resin comprises a (meth)acrylateresin.

Additives

In some embodiments, the curable resin further comprises 0.1 wt. % to 10wt .% of a photoinitiator. Photinitiators, may be added to the curableresin to facilitate polymerization of the curable resin. Thephotoinitators are typically designed to be activated by the exposure toactinic radiation. Photoinitiators include, but are not limited to,those available under the trade designations “IRGACURE” and “DAROCUR”from BASF Corp, Florham Park, N.J., and include 1-hydroxy cyclohexylphenyl ketone (trade designation “IRGACURE 184”),2,2-dimethoxy-1,2-diphenylethan-1-one (trade designation “IRGACURE651”), Bis(2,4,6-trimethyl benzoyl)phenylphosphineoxide (tradedesignation “IRGACURE819”),1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one(trade designation “IRGACURE 2959”),2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (tradedesignation “IRGACURE 369”),2-methyl-1[4-(methylthio)phenyl]1-2-morpholinopropan-1-one (tradedesignation “IRGACURE 907”), and 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade designation “DAROCUR 1173”).

Other additives may optionally be included in the curable resin and,subsequently, the coating. Additives include, but are not limited tonanoparticles dispersed throughout the curable resin, pigments,surfactants, solvents, wetting aids, slip agents, leveling agents,tackifiers, toughening agents, reinforcing agents, fire retardants,antioxidants, antistatic agents (e.g., trimethylacryloxyethyl ammoniumbis(trifluoromethyl)sulfonimide), stabilizers, and combinations thereof.The additives are added in amounts sufficient to obtain the desired endproperties. In some embodiments, the amount of additive in the curableresin is from 0.1 wt. % to wt. %, 0.1 wt. % to 20 wt. %, or 0.1 wt. % to10 wt. %.

Coating Composition

A coating composition of the present disclosure may be prepared by themethods known to those of ordinary skill in the relevant arts and usingthe materials described above. The methods disclosed in the Examplesbelow and shown in FIG. 2 can be scaled for roll-to-roll processing byone of ordinary skill in the relevant arts as shown, for example, inFIG. 6 . As shown in FIG. 6 , the curable resin layer is typicallycontacted with a substrate before curing to provide a laminate. Avariety of materials are suitable for use as the substrate, includingboth flexible materials and materials that are more rigid. The substratemay include, for example, a polymeric film, a primed polymeric film, ametal foil, a cloth (e.g., a textile), a paper, a vulcanized fiber, anonwoven material and treated versions thereof, and combinationsthereof. The substrate may be a polymeric film or treated polymericfilm. Examples of such films include, but are not limited to, polyesterfilm (e.g., polyethylene terephthalate film, polybutylene terephthalatefilm, polybutylene succinate film, polylactic acid film), co-polyesterfilm, polyimide film, polyamide film, polyurethane film, polycarbonatefilm, polyvinyl chloride film, polyvinyl alcohol film, polypropylenefilm (e.g., biaxially oriented polypropylene), polyethylene film,poly(methyl methacrylate) film, and the like. In some preferredembodiments, the substrate is a polymeric film such as, for example, apolycarbonate film. As shown in FIG. 7 , such laminates may undergofurther processing such as, for example, thermoforming, and may beincorporated into articles such as, for example, lenses to provideabrasion resistance. Additional articles that may include the laminateinclude, but are not limited to, automotive interior fixtures andelectronics cases. In preferred embodiments, hardcoats preparedaccording to methods of the present disclosure exhibit a delta haze lessthan 25, less than 10, less than 5, less than 2.5, or less than 2according to ASTM D1044-13.

Objects and advantages of this disclosure are further illustrated by thefollowing non-limiting examples, but the particular materials andamounts thereof recited in these examples, as well as other conditionsand details, should not be construed to unduly limit this disclosure.

Objects and advantages of this disclosure are further illustrated by thefollowing non-limiting examples, but the particular materials andamounts thereof recited in these examples, as well as other conditionsand details, should not be construed to unduly limit this disclosure.

EXAMPLES

Unless otherwise noted, all parts, percentages, ratios, etc. in theExamples and the rest of the specification are by weight.

TABLE 1 Materials Abbreviation Description and Source SR420 Trimethylcyclohexyl acrylate from Sartomer, Exton, Pennsylvania, as SR420 SR506Isobornyl acrylate available from Sartomer as SR506 SR285Tetrahydrofurfuryl acrylate available from Sartomer as SR285 SR9035Ethoxylated (15) trimethylolpropane triacrylate available from Sartomeras SR9035 IRG819 Bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxideavailable from BASF Corporation, Florham Park, New Jersey, as IRGACURE819 PET1 2 mil (51 micron) polyethylene terephthalate film availablefrom 3M Company, St. Paul, Minnesota, as SCOTCHPAK POLYESTER FILM SR2381,6 hexanediol diacrylate available from Sartomer as SR238 SR295Pentaerythritol tetraacrylate available from Sartomer as SR295 IRG1841-hydroxycyclohexyl phenyl ketone available from BASF Corporation asIRGACURE 184 IRGTPO 2,4,6-trimethylbenzoyl-diphenyl phosphine oxideavailable from BASF Corporation as IRGACURE TPO NBYK3605 Dispersion ofsurface-treated silica nanoparticles in hexanediol diacrylate, 50%nanoparticle content, 20 nm particle size, available from BYK USAIncorporated, Wallingford, Connecticut, as NANOBYK-3605 PC1 5 mil (127micron) polycarbonate film available from Sabic Americas Inc., Houston,Texas, as LEXAN 8010-112MC EB4513 Trifunctional urethane acrylateoligomer available from Allnex, Alpharetta, Georgia, as EBECRYL 4513CN991 Difunctional urethane acrylate oligomer available from Sartomer asCN991 ESACURE Difunctional alpha hydroxy ketone available from IGMResins, Charlotte, North ONE Carolina, as ESACURE ONE PP1 2 mil (51micron) polypropylene film available from Inteplast Group, Livingston,New Jersey, as VT60A PP2 2 mil (51 micron) polypropylene film availablefrom Inteplast Group, as TT50T PP3 2 mil (51 micron) polypropylene filmavailable from 3M Company, as the backing for SCOTCH Heavy Dutypackaging tape (3850) IPA-ST Silica nanoparticles dispersed inisopropanol, 10-15 nm particle size. Supplied at 30% solids from NissanChemical America Corporation, Houston, Texas, as IPA-ST IPA-ST-L Silicananoparticles dispersed in isopropanol, 40-50 nm particle size. Suppliedat 30% solids from Nissan Chemical America Corporation, as IPA-ST-LIPA-ST-ZL Silica nanoparticles dispersed in isopropanol, 70-100 nmparticle size. Supplied at 30% solids from Nissan Chemical AmericaCorporation, as IPA-ST-ZL IPA-ST-UP Elongated silica nanoparticlesdispersed in isopropanol, 9-15 nm particle strand diameter and 40-100 nmoverall length. Supplied at 15% solids from Nissan Chemical AmericaCorporation, as IPA-ST-UP PGME Propylene glycol methyl ether or1-methoxy-2-propanol available from Sigma Aldrich, St. Louis, MissouriNALCO 2326 Colloidal silica having a nominal particle size of 5 nmobtained under the trade designation NALCO 2326 from Nalco Company,Bedford Park, IL NALCO 2327 Colloidal silica having a nominal particlesize of 20 nm obtained under the trade designation NALCO 2327 from NalcoCompany NALCO 2329 Colloidal silica having a nominal particle size of 75nm obtained under the trade designation NALCO 2329 from Nalco CompanyMP1040 Colloidal silica having a nominal particle size of 100 nmobtained under the trade designation MP1040 from Nissan Chemical AmericaCorporation MP2040 Colloidal silica having a nominal particle size of190 nm obtained under the trade designation MP2040 from Nissan ChemicalAmerica Corporation MPS 3-(methacryloyloxy)propyltrimethoxy silaneobtained from Alfa Aesar, Ward Hill, MAMethods Preparation of Surface-Modified Silica Nanoparticles: Silicananoparticles of 190 nm, 100 nm, nm, 20 nm and 5 nm diameters weresurface-modified according to the procedures disclosed in PreparatoryExamples 2, 7, and 9 of U.S. Pat. Pub. 2015/0017386 A1 (Kolb et al.) Thesurface treatments were all 100% MPS,3-(methacryloyloxy)propyltrimethoxy silane. Particle sizes and materialsincluded: MP2040 for 190 nm silica nanoparticles, MP1040 for 100 nmsilica nanoparticles, NALCO 2329 for 75 nm silica nanoparticles, NALCO2327 for 20 nm silica nanoparticles, and NALCO 2326 for 5 nm silicananoparticles. Preparation of Scanning Electron Microsope (“SEM”)Images: The imaged samples were Cryo-scalpel Loop cut, mounted ontocross section stubs, moderately coated with Au/Pd to prevent chargingand imaged on the 8230 Hitachi Microscope. 3 kV imaging voltage (normalprobe current), 15 kx-100 kx Magnification. FIG. 4 is an SEM image of across-section of an article prepared according to the presentdisclosure. FIG. 5 is an SEM image of a cross-section of the top layer(i.e., the nanoparticle layer) of the article of FIG. 4 .

Examples 1-4 Different Nanoparticles Transferred from Polymeric Film PP1Using Coating Solution PE1

TABLE 2 Composition of Preparatory Example 1 for Examples 1-8Preparatory Example SR238 SR9035 IRG184 IRGTPO PE1 49 49 0.8 1.2

UV-curable coating solution PE1 was prepared by dissolving aphoto-initiator blend (40/60 blend of IRG184 and IRGTPO; 2 wt. %) into aUV-curable resin blend (50/50 blend of

SR238B and SR9035; 98 wt. %) as supplied from the manufacturer,according to Table 2.

TABLE 3 Composition of Preparatory Examples 2-5 for Examples 1-12Dilution Preparatory Nanoparticle Wt. % as Factor Final Wt. ExampleIdentity Supplied by Weight % SiO₂ PE2 IPA-ST 30 1:4 7.5 PE3 IPA-ST-L 301:4 7.5 PE4 IPA-ST-ZL 30 1:4 7.5 PE5 IPA-ST-UP 15 1:2 7.5

Nanoparticle dispersions were prepared by diluting IPA-ST, IPA-ST-L,IPA-ST-ZL, and IPA-ST-UP as supplied from the manufacturer to 7.5 weightpercent with isopropanol, according to Table 3. The nanoparticledispersions were mixed with high agitation on a vortex mixer. PP1, usedas received, was cut into an 8 in×10 in (20 cm×25 cm) sheet. The PP1sheet was placed upon a flat glass surface. Each nanoparticledispersion, PE2-PES, from Table 3 above was coated onto a separate sheetof PP1 with Mayer rod #6 (R D Specialties, Webster, N.Y.). Each of theMayer rod coatings was approximately 7 in×9 in (18 cm×23 cm). Allcoatings were allowed to air dry for 2-24 hours at room temperature.

Once dried, the nanoparticle coatings were trimmed to approximately 6in×9 in (15 cm×23 cm). Additionally, one sheet of PP1 without anycoating was similarly trimmed. Each of the nanoparticle coatings and theuncoated PP1 was placed upon a flat glass surface with the nanoparticleside up (where applicable). A 6 in×9 in (15 cm×23 cm) piece of PET1 filmwas gently laid upon the dried nanoparticle coating with the primed sideof PET1 against the nanoparticle coating. In the case of CE1, the primedside of PET1 was against the uncoated PP1. PET1 was carefully rolledback from the nanoparticle coating (where applicable) and over Mayer rod#6. A 0.5 mL bead of PE1 was deposited onto the nanoparticle coatingwith a disposable pipette. The Mayer rod was moved across the surface ofthe nanoparticle coating to spread the PE1 while simultaneouslylaminating PET1 to the nanoparticle coating. This technique, wherein theMayer rod never directly touches the coating formula, PE1, eliminatesair from becoming entrained in the laminate. In the case of CE1, thecoating formula, PE1, is spread between PET1 and an uncoated sheet ofPP1.

The laminates were placed under a medium pressure mercury D bulbradiation source, with the PET1 film being the topmost layer. The UVprocessor with the medium pressure mercury D bulb radiation source was aHERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHT HAMMER 6 ModelLH 500 W/in (200 W/cm) power source with the output power set to 100%.The laminates were carried through the UV processor by a conveyor beltsystem at a speed of 40 feet/minute (12.2 m/minute). The PET1 film andthe cured coating with captured nanoparticles (where applicable) werepeeled as a unit from the surface of the PP1 sheet.

The initial transmission and haze of Examples 1-4 and CE1 were measuredwith a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). Results are shown in Table 4.

The Examples were tested for abrasion resistance according to ASTMD1044-13. Two specimens for each condition were tested and the resultsaveraged. CS-10F abrasive wheels, 100 cycles, 500 gram load, 60cycles/min. The post-abrasion (final) haze and transmission weremeasured on the same instrument. Results are shown in Table 4.

TABLE 4 Hardcoat Testing Nano- Average Average Average Average particleInitial Initial Final Final Delta Delta Example Layer Transmission HazeTransmission Haze Transmission Haze CE1 None 92.2 1.19 91.0 5.90 −1.24.71 1 IPA-ST 92.2 1.21 91.1 11.7 −1.1 10.5 (PE2) 2 IPA-ST-L 92.4 1.1891.4 7.93 −1.0 6.75 (PE3) 3 IPA-ST-ZL 92.4 1.15 91.4 12.7 −1.0 11.6(PE4) 4 IPA-ST-UP 92.3 1.22 91.3 4.00 −1.0 2.78 (PE5)

Examples 5-8 Different Nanoparticles Transferred from Polymeric Film PP2Using Coating Solution PE1

PP2, used as received, was cut into an 8 in×10 in (20 cm×25 cm) sheet.The PP2 sheet was placed upon a flat glass surface. Each nanoparticledispersion, PE2-PES, from Table 3 above was coated onto a separate sheetof PP2 with Mayer rod #6 (R D Specialties, Webster, N.Y.). Each of theMayer rod coatings was approximately 7 in×9 in (18 cm×23 cm). Allcoatings were allowed to air dry for 2-24 hours at room temperature.

Once dried, the nanoparticle coatings were trimmed to approximately 6in×9 in (15 cm×23 cm). Additionally, one sheet of PP2 without anycoating was similarly trimmed. Each of the nanoparticle coatings and theuncoated PP2 was placed upon a flat glass surface with the nanoparticleside up (where applicable). A 6 in×9 in (15 cm×23 cm) piece of PET1 filmwas gently laid upon the dried nanoparticle coating with the primed sideof PET1 against the nanoparticle coating. In the case of CE2, the primedside of PET1 was against the uncoated PP2. PET1 was carefully rolledback from the nanoparticle coating (where applicable) and over Mayer rod#6. A 0.5 mL bead of PE1 was deposited onto the nanoparticle coatingwith a disposable pipette. The Mayer rod was moved across the surface ofthe nanoparticle coating to spread the PE1 while simultaneouslylaminating PET1 to the nanoparticle coating. This technique, wherein theMayer rod never directly touches the coating formula, PE1, eliminatesair from becoming entrained in the laminate. In the case of CE2, thecoating formula, PE1, is spread between PET1 and an uncoated sheet ofPP2.

The laminates were placed under a medium pressure mercury D bulbradiation source, with the PET1 film being the topmost layer. The UVprocessor with the medium pressure mercury D bulb radiation source was aHERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHT HAMMER 6 ModelLH6 500 W/in (200 W/cm) power source with the output power set to 100%.The laminates were carried through the UV processor by a conveyor beltsystem at a speed of 40 feet/minute (12.2 m/minute). The PET1 film andthe cured coating with captured nanoparticles (where applicable) werepeeled as a unit from the surface of the PP2 sheet.

The initial transmission and haze of Examples 5-8 and CE2 were measuredwith a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). Results are shown in Table 5.

The Examples were tested for abrasion resistance according to ASTMD1044-13. Two specimens for each condition were tested and the resultsaveraged. CS-10F abrasive wheels, 100 cycles, 500 gram load, 60cycles/min. The post-abrasion (final) haze and transmission weremeasured on the same instrument. Results are shown in Table 5.

TABLE 5 Hardcoat Testing Nano- Average Average Average Average particleInitial Initial Final Final Delta Delta Example Layer Transmission HazeTransmission Haze Transmission Haze CE2 None 92.1 1.25 91.1 4.61 −1.03.36 5 IPA-ST 92.4 1.19 91.4 5.35 −1.0 4.16 (PE2) 6 IPA-ST-L 92.4 1.1491.3 7.68 −1.1 6.54 (PE3) 7 IPA-ST-ZL 92.3 1.16 91.5 10.8 −0.8 9.64(PE4) 8 IPA-ST-UP 92.3 1.34 91.2 3.57 −1.1 2.23 (PE5)

Examples 9-12 Different Nanoparticles Transferred from Polymeric FilmPP1 Using Coating Solution PE6

TABLE 6 Composition of Preparatory Example 6 for Examples 9-12Preparatory Example SR238 SR295 IRG184 IRGTPO PE6 49 49 0.8 1.2

PP1, used as received, was cut into an 8 in×10 in (20 cm×25 cm) sheet.The PP1 sheet was placed upon a flat glass surface. Each nanoparticledispersion, PE2-PES, from Table 3 above was coated onto a separate sheetof PP1 with Mayer rod #6 (R D Specialties, Webster, N.Y.). Each of theMayer rod coatings was approximately 7 in×9 in (18 cm×23 cm). Allcoatings were allowed to air dry for 2-24 hours at room temperature.

Once dried, the nanoparticle coatings were trimmed to approximately 6in×9 in (15 cm×23 cm). Additionally, one sheet of PP1 without anycoating was similarly trimmed. Each of the nanoparticle coatings and theuncoated PP1 was placed upon a flat glass surface with the nanoparticleside up (where applicable). A 6 in×9 in (15 cm×23 cm) piece of PET1 filmwas gently laid upon the dried nanoparticle coating with the primed sideof PET1 against the nanoparticle coating. In the case of CE3, the primedside of PET1 was against the uncoated PP1. PET1 was carefully rolledback from the nanoparticle coating (where applicable) and over

Mayer rod #6. A 0.5 mL bead of PE6 was deposited onto the nanoparticlecoating with a disposable pipette. The Mayer rod was moved across thesurface of the nanoparticle coating to spread the PE6 whilesimultaneously laminating PET1 to the nanoparticle coating. Thistechnique, wherein the Mayer rod never directly touches the coatingformula, PE6, eliminates air from becoming entrained in the laminate. Inthe case of CE3, the coating formula, PE6, is spread between PET1 and anuncoated sheet of PP1.

The laminates were placed under a medium pressure mercury D bulbradiation source, with the PET1 film being the topmost layer. The UVprocessor with the medium pressure mercury D bulb radiation source was aHERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHT HAMMER 6 ModelLH6 500 W/in (200 W/cm) power source with the output power set to 100%.The laminates were carried through the UV processor by a conveyor beltsystem at a speed of 40 feet/minute (12.2 m/minute). The PET1 film andthe cured coating with captured nanoparticles (where applicable) werepeeled as a unit from the surface of the PP1 sheet. The initialtransmission and haze of Examples 9-12 and CE3 were measured with a BYK

HAZE GARD I instrument (BYK Instruments, Geretsried, Germany). Resultsare shown in Table 7. The Examples were tested for abrasion resistanceaccording to ASTM D1044-13. Two specimens for each condition were testedand the results averaged. CS-10F abrasive wheels, 100 cycles, 500 gramload, 60 cycles/min. The post-abrasion (final) haze and transmissionwere measured on the same instrument. Results are shown in Table 7.

TABLE 7 Hardcoat Testing Nano- Average Average Average Average particleInitial Initial Final Final Delta Delta Example Layer Transmission HazeTransmission Haze Transmission Haze CE3 None 92.0 1.24 90.8 6.11 −1.24.87 9 IPA-ST 92.4 1.18 90.8 11.8 −1.6 10.6 (PE2) 10 IPA-ST-L 92.4 1.1191.1 6.12 −1.3 5.01 (PE3) 11 IPA-ST-ZL 92.5 1.13 91.2 7.50 −1.3 6.37(PE4) 12 IPA-ST-UP 92.4 1.20 91.0 5.17 −1.4 3.97 (PE5)

Examples 13-21 Nanoparticle Dispersions Coated onto Donor Polymeric Filmat Different Concentrations

TABLE 8 Composition of Preparatory Examples 7-13 for Examples 13-21Dilution Preparatory Nanoparticle Wt. % as Factor Final Wt. ExampleIdentity Supplied by Weight % SiO₂ PE7 IPA-ST-L 30 1:40 0.75 PE8IPA-ST-L 30 1:12 2.5 PE9 IPA-ST-L 30 1:2  15 PE10 IPA-ST-L 30 None 30PE11 IPA-ST-UP 15 1:20 0.75 PE12 IPA-ST-UP 15 1:6  2.5 PE13 IPA-ST-UP 15None 15

Nanoparticle dispersions were prepared by diluting IPA-ST-L andIPA-ST-UP with isopropanol, according to Table 8. The nanoparticledispersions were mixed with high agitation on a vortex mixer. PP3, usedas received, was cut into an 8 in×12 in (20 cm×30.5 cm) sheet. The PP3sheet was placed upon a flat glass surface. Each nanoparticledispersion, PE7-PE13, from Table 8 above, along with PE3 and PE5 wascoated onto a separate sheet of PP3 with Mayer rod #6 (R D Specialties,Webster, N.Y.). Each of the Mayer rod coatings was approximately 7 in×10in (18 cm×25 cm). All coatings were allowed to air dry for 2-24 hours atroom temperature.

Once dried, the nanoparticle coatings were trimmed to approximately 6in×10 in (15 cm×25 cm). Additionally, one sheet of PP3 without anycoating was similarly trimmed. Each of the nanoparticle coatings and theblank PP3 was placed upon a flat glass surface with the nanoparticleside up (where applicable). A 6 in×9 in (15 cm×23 cm) piece of PET1 filmwas gently laid upon the dried nanoparticle coating with the primed sideof PET1 against the nanoparticle coating. In the case of CE4, the primedside of PET1 was against the uncoated PP3. PET1 was carefully rolledback from the nanoparticle coating (where applicable) and over Mayer rod#6. A 0.5 mL bead of PE1 was deposited onto the nanoparticle coatingwith a disposable pipette. The Mayer rod was moved across the surface ofthe nanoparticle coating to spread the PE1 while simultaneouslylaminating PET1 to the nanoparticle coating. This technique, wherein theMayer rod never directly touches the coating formula, PE1, eliminatesair from becoming entrained in the laminate. In the case of CE4, thecoating formula, PE1, is spread between PET1 and an uncoated sheet ofPP3.

The laminates were placed under a medium pressure mercury D bulbradiation source, with the PET1 film being the topmost layer. The UVprocessor with the medium pressure mercury D bulb radiation source was aHERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHT HAMMER 6 ModelLH6 500 W/in (200 W/cm) power source with the output power set to 100%.The laminates were carried through the UV processor by a conveyor beltsystem at a speed of 40 feet/minute (12.2 m/minute). The PET1 film andthe cured coating with captured nanoparticles (where applicable) werepeeled as a unit from the surface of the PP3. SEM analysis revealed thatthe nanoparticles that were removed from the surface of PP3 becameconcentrated at the surface of the cured coating that had been adjacentto the PP3 film.

The initial transmission and haze of Examples 13-21 and CE4 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). Results are shown in Table 9. The Examples were tested forabrasion resistance according to ASTM D1044-13. Two specimens for eachcondition were tested and the results averaged. CS-10F abrasive wheels,100 cycles, 500 gram load, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument. Results are shownin Table 9.

TABLE 9 Hardcoat Testing Nano- particle Nano- Concentration AverageAverage Average Average particle in Transfer Initial Initial Final FinalDelta Delta Example Layer Layer Transmission Haze Transmission HazeTransmission Haze CE4 None N/A 92.3 0.41 91.2 4.25 −1.1 3.84 13 IPA-ST-L0.75%  92.6 0.40 91.3 4.39 −1.3 3.99 (PE7) 14 IPA-ST-L 2.5% 92.3 0.3891.2 5.45 −1.1 5.07 (PE8) 15 IPA-ST-L 7.5% 92.5 0.37 91.5 8.13 −1.0 7.76(PE3) 16 IPA-ST-L  15% 92.5 0.40 91.4 6.63 −1.1 6.23 (PE9) 17 IPA-ST-L 30% 92.1 2.23 91.3 13.6 −0.8 11.4 (PE10) 18 IPA-ST-UP 0.75%  92.3 0.4591.3 3.54 −1.0 3.09 (PE11) 19 IPA-ST-UP 2.5% 92.4 0.41 91.3 4.77 −1.14.36 (PE12) 20 IPA-ST-UP 7.5% 92.4 0.44 91.4 3.26 −1.0 2.82 (PE5) 21IPA-ST-UP  15% 92.4 0.47 91.5 3.99 −0.9 3.52 (PE13)

Comparative Examples 5-12 Coatings with IPA-ST-L Nanoparticles in theBulk Coating Solution

TABLE 10 Composition of Preparatory Examples 22-29 for ComparativeExamples 5-12 Preparatory IPA- Isopro- Example SR238 SR9035 IRG184IRGTPO ST-L panol PE14 24.5 24.5 0.4 0.6 0 50 PE15 23 23 0.4 0.6 10 43PE16 21.5 21.5 0.4 0.6 20 36 PE17 20 20 0.4 0.6 30 29 PE18 18.5 18.5 0.40.6 40 22 PE19 17 17 0.4 0.6 50 15 PE20 15.5 15.5 0.4 0.6 60 8 PE21 1414 0.4 0.6 70 1

UV-curable coating solutions PE14-21 were prepared according to Table10. UV-curable coating solutions PE14-21 were mixed on a jar rollerovernight. The UV-curable coating solutions from Table 10 above werecoated onto the primed side of PET1 film. Each of the UV-curable coatingsolutions PE14-PE21 was coated with Mayer rod #9 (R D Specialties,Webster, N.Y.). Each of the Mayer rod coatings was approximately 5 in×7in (12.7 cm×17.8 cm); a size sufficient for Taber abrasion testing. PET1films with PE14-21 coated thereupon were dried for 45 seconds at 80° C.The dried coatings were placed under a medium pressure mercury H bulbradiation source, with the UV-curable coating being the topmost layer.The UV processor with the medium pressure mercury H bulb radiationsource was a HERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHTHAMMER 6 Model LH6 500 W/in (200 W/cm) power source. An H bulb was usedat 100% power setting, and the process area was purged with nitrogengas. The film/coating was carried through the UV processor by a conveyorbelt system at a speed of 40 ft/min (12.192 m/min).

The initial transmission and haze of Comparative Examples 5-12 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). Results are shown in Table 11. The Examples were tested forabrasion resistance according to ASTM D1044-13. Two specimens for eachcondition were tested and the results averaged. CS-10F abrasive wheels,100 cycles, 500 gram load, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument. Results are shownin Table 11.

TABLE 11 Hardcoat Testing UV-Curable Average Average Average AverageCoating Initial Initial Final Final Delta Delta Example SolutionTransmission Haze Transmission Haze Transmission Haze CE5 PE14 92.4 0.2191.5 3.21 −0.9 3.00 CE6 PE15 92.4 0.20 91.3 3.31 −1.1 3.11 CE7 PE16 92.30.22 91.2 3.71 −1.1 3.49 CE8 PE17 92.4 0.21 91.3 4.01 −1.1 3.80 CE9 PE1892.4 0.25 91.3 3.80 −1.1 3.55 CE10 PE19 92.5 0.22 91.2 4.62 −1.3 4.40CE11 PE20 92.4 0.21 91.3 5.31 −1.1 5.10 CE12 PE21 92.5 0.21 91.3 7.37−1.2 7.16

Comparative Examples 13-21 Coatings with IPA-ST-UP Nanoparticles in theBulk Coating Solution

TABLE 12 Composition of Preparatory Examples 22-30 for ComparativeExamples 13-21 Preparatory IPA- Isopro- Example SR238 SR9035 IRG184IRGTPO ST-UP panol PE22 14.7 14.7 0.24 0.36 0 70 PE23 13.95 13.95 0.240.36 10 61.5 PE24 13.2 13.2 0.24 0.36 20 53 PE25 12.45 12.45 0.24 0.3630 44.5 PE26 11.7 11.7 0.24 0.36 40 36 PE27 10.95 10.95 0.24 0.36 5027.5 PE28 10.2 10.2 0.24 0.36 60 19 PE29 9.45 9.45 0.24 0.36 70 10.5PE30 8.7 8.7 0.24 0.36 80 2

UV-curable coating solutions PE22-30 were prepared according to Table12. UV-curable coating solutions PE22-30 were mixed on a jar rollerovernight. The UV-curable coating solutions from Table 12 above werecoated onto the primed side of PET1 film. Each of the UV-curable coatingsolutions PE22-30 was coated with Mayer rod #14 (R D Specialties,Webster, N.Y.). Each of the Mayer rod coatings was approximately 5 in×7in (12.7 cm×17.8 cm); a size sufficient for Taber abrasion testing. PET1films with PE22-30 coated thereupon were dried for 45 seconds at 80° C.The dried coatings were placed under a medium pressure mercury H bulbradiation source, with the UV-curable coating being the topmost layer.The UV processor with the medium pressure mercury H bulb radiationsource was a HERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHTHAMMER 6 Model LH6 500 W/in (200 W/cm) power source. An H bulb was usedat 100% power setting, and the process area was purged with nitrogengas. The film/coating was carried through the UV processor by a conveyorbelt system at a speed of 40 ft/min (12.192 m/min).

The initial transmission and haze of Comparative Examples 13-21 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). Results are shown in Table 13. The Examples were tested forabrasion resistance according to ASTM D1044-13.

Two specimens for each condition were tested and the results averaged.CS-10F abrasive wheels, 100 cycles, 500 g load, 60 cycles/min. Thepost-abrasion (final) haze and transmission were measured on the sameinstrument. Results are shown in Table 13.

TABLE 13 Hardcoat Testing UV-Curable Average Average Average AverageCoating Initial Initial Final Final Delta Delta Example SolutionTransmission Haze Transmission Haze Transmission Haze CE13 PE22 92.30.22 91.3 4.30 −1.0 4.08 CE14 PE23 92.3 0.86 91.2 6.44 −1.1 5.58 CE15PE24 92.3 0.66 91.2 6.42 −1.1 5.76 CE16 PE25 92.3 0.65 91.1 5.59 −1.24.94 CE17 PE26 92.3 0.44 91.1 5.13 −1.2 4.69 CE18 PE27 92.2 0.39 91.24.10 −1.0 3.72 CE19 PE28 92.4 0.34 91.3 3.04 −1.1 2.70 CE20 PE29 92.60.51 91.4 3.48 −1.2 2.97 CE21 PE30 92.6 0.41 91.5 3.25 −1.1 2.84

Examples 22-25 Thermoformable Compositions

TABLE 14 Composition of Preparatory Examples 39-46 for Examples 22-25Prep. ESACURE Ex. EB4513 CN991 SR420 SR506 SR238 SR285 NBYK3605 IRG819ONE PE39 68 0 10 5 10 5 0 1 1 PE40 0 68 10 5 10 5 0 1 1 PE41 66 0 10 5 85 4 1 1 PE42 0 66 10 5 8 5 4 1 1 PE43 63 0 10 5 5 5 10 1 1 PE44 0 63 105 5 5 10 1 1 PE45 58 0 10 5 0 5 20 1 1 PE46 0 58 10 5 0 5 20 1 1

UV-curable coating solutions PE39-46 were prepared by dissolving aphoto-initiator blend (50/50 blend of IRG819 and ESACURE ONE; 2 wt.%)into a UV-curable resin blend as 10 supplied from the manufacturer,according to Table 14. PP3,used as received, was cut into an 12 in×12 in(30.5 cm×30.5 cm) sheet. The PP3 sheet was placed upon a flat glasssurface. Each nanoparticle dispersion, PE3, PES, PE9 and PE13, from thetables above was coated onto a separate sheet of PP3 with Mayer rod #6(R D Specialties, Webster, N.Y.). Each of the Mayer rod coatings wasapproximately 10 in×10 in (25 cm×25 cm). All coatings were allowed toair dry for 2-24 hours at room temperature. Once dried, the nanoparticlecoatings were trimmed to approximately 10 in×10 in (25 cm×25 cm).Additionally, eight sheets of PP3 without any coating were similarlytrimmed. Each of the nanoparticle coatings and the blank PP3 sheets wasplaced upon a flat glass surface with the nanoparticle side up (whereapplicable). A 10 in×10 in (25 cm×25 cm) piece of PC1 film was gentlylaid upon the dried nanoparticle coating with a side of PCI against thenanoparticle coating. In the cases of CE23, CE24, CE29, CE30, CE31,CE32, CE33 and CE34, the primed side of PC1 was against the uncoatedPP3. PC1 was carefully rolled back from the nanoparticle coating (whereapplicable) and over Mayer rod #6. A 1 mL bead of each PE39 and PE40 wasdeposited onto the nanoparticle coating with a disposable pipette. TheMayer rod was moved across the surface of the nanoparticle coating inorder to effect the spreading of PE39 or PE40 while simultaneouslylaminating PC1 to the nanoparticle coating. This technique, wherein theMayer rod never directly touches the coating formulas, PE39 or PE40,eliminates air from becoming entrained in the laminate. In the cases ofCE23, CE24, CE29, CE30, CE31, CE32, CE33, CE34, the coating formulas,PE39-46, are spread between PCI and an uncoated sheet of PP3. Thelaminates were placed under combination medium pressure mercury D and Hbulb radiation sources, with the PP3 film being the topmost layer. TheUV processor with the medium pressure mercury D and H bulb radiationsources was a HERAEUS FUSION UV SYSTEMS INC. unit equipped with a LIGHTHAMMER 10 Model LH10 600 W/in (240 W/cm) power source with the outputpower set to 100%. The laminates were carried through the UV processorby a conveyor belt system at a speed of 60 feet/minute (18.3 m/minute).The PC1 film and the cured coating with captured nanoparticles (whereapplicable) were peeled as a unit from the surface of the PP3.

Thermoforming Process

Samples were formed using HY-TECH ACCUFORM IL-50 thermoforming equipment(Hy-Tech Forming Systems, Phoenix, Arizona, USA) using the processconditions listed in Table 15. The mold geometry used is described asthe 8-base geometry, made of PORTEC METAPOR HD 210 AL (Portec, Aadorf,Switzerland) to allow air to vent from below the film without causinglarge witness marks from vent locations. The 8-base thermoforming mold,shown in FIGS. 8A and 8B, is accompanied by a matching 8-base injectionmold described below.

ACCUFORM IL-50 Machine Layout: an upper platen that is heated usingresistive heating elements to a set temperature controlled to +/−10 F.,this platen travels vertically to clamp the film between the upper andlower platen to make a pressure chamber. The lower platen has the moldgeometry mounted; in this case a negative mold version of the 8-basethermoforming mold was used.

ACCUFORM IL-50 Process: the film is placed on top of the lower platen,completely covering the mold area allowing for a seal to form using thefilm itself as a gasket between the upper and lower platens. When thecycle is started the clamp closes, the clamp of the machine is designedto always use 50 tons of clamp force to maintain parting line seal whenclosed and under pressure. When the clamp closes the preheat cyclebegins and the preheat timer starts counting down, the film is blown upagainst the upper platen using the preheat pressure setpoint, this keepsthe film in intimate contact with the heated upper platen. When thepreheat timer expires, the pressure is vented to atmosphere and the formpressure is applied through the upper platen and on the top side of thefilm, this forces the heated film downward against the mold surfacereplicating the mold geometry. When the form timer expires, the formpressure is vented to atmosphere for the release time. The clamp thenopens when the release timer expires. This completes the cycle.

TABLE 15 Thermoforming Process Conditions Setting Imperial SI HeatedPlaten Temperature 320 F. 160 C. Mold Temperature 80 F. 26.7 C. PreheatTime 6 s Preheat Pressure 60 psi 414 Kpa Form Time 6 s Release Time 1 s

Insert Molding

Thermoformed 8-base samples were trimmed using scissors to a dimensionthat was smaller than the optical surface of the injection mold. Thiswas traced onto each film using the optical insert as a guide.

The samples were held into place against the optical surface of theconvex side of the lens using static pinning, with a SIMCO-IONCHARGEMASTER VCM30 (Simco-Ion, Hatfield, Pa., USA) set to −11 Kv tocharge the film and cause it to cling to the grounded tool surface.

The injection molding machine used was a ENGEL EM 310/180T (Engel,Schwertberg, Austria) all electric injection 180 ton injection moldingmachine, with a 25 mm screw/barrel. The injection molding processspecific conditions are listed in Table 16, the process outline is asfollows. The film is placed into the stationary side of the mold(concave optical mold cavity) and held in place with static pinning bymanually placing the film in the desired location and slowly passing aSIMCO-ION LINEAR PINNER over top of the sample to completely charge thesurface. The injection molding cycle is started, the mold is closed,material is injected through the sprue, runner, and gate into the partduring the fill phase with a set injection velocity until the part is99% full (Velocity Pressure Transfer—VPT). At the VPT the press switchescontrol logic and stops using velocity control and begins the hold phaseusing pressure control of the screw, this fills the remaining 1% of thecavity and maintains cavity pressure while the part is cooling until thegate freezes (hold time). After the gate freezes the cooling timerstarts and the screw begins to rotate to build the next shot of materialfor the subsequent cycle. After the cooling timer expires the moldopens, and the ejector system cycles to remove the part from the cavity.

The ejector system was programmed to remain forward and not fully ejectthe part to prevent it falling and getting damaged. The operator doorwas opened, the part was removed and packaged for transport.

TABLE 16 Engel EM 310/180T Molding Machine Process Conditions SettingImperial SI Resin Mitsubishi Iupilon - HL4002 Velocity 5 in/s 127 mm/sFill time 0.37 s   Pressure at switchover 11500 Psi 79290 Kpa Screw backposition 2 in 50.8 mm Screw suckback 0.1 in 2.54 mm Transfer Position0.39 in 9.9 mm Cushion Position 0.239 in 6.07 mm Screw RPM 120 BackPressure 1000 Psi 6895 Kpa Hold Time 16 s Hold Pressure 4000 Psi 27579Kpa Cool Time 30 s Clamp Force 80 US Ton 712 Kn Screw Size 0.984 in 25mm Mold set temperature A 200 F. 93.3 C. Mold set temperature B 200 F.93.3 C. Nozzle Temperature 530 F. 277 C. Barrel Temperature 1 540 F. 232C. Barrel Temperature 2 480 F. 249 C. Barrel Temperature 3 470 F. 443 C.Feed throat Temperature 175 F. 79 C.

TABLE 17 Thermoforming and Insert Molding Outcomes for Examples 22-25and Comparative Examples 22-34 Example Nano-silica 8-base Thermo- InsertMolding Number Example Description Disposition forming Result ResultCE22 Polycarbonate Film, None 20/20 formed 18/18 mold fine no coat CE23PC Film + Ebecryl None 6/6 formed 3/6 cracked 4513 coat (PE39) CE24 PCFilm + CN991 None 6/6 formed 6/6 molded fine coating (PE40) (1 fouled byold resin; 1 insert damaged) 22 PC Film + Eb 4513 Surface, 7.5% 3/4formed 3/3 molded fine coating (PE39) + parent coating IPA-ST-UPnanoparticles conc. (PE5) 23 PC Film + Eb4513 Surface, 7.5% 4/4 formed2/4 cracked coating (PE39) + parent coating IPA-ST-L nanoparticles conc.(PE3) 24 PC Film + CN991 Surface, 7.5% 4/4 formed 4/4 molded finecoating (PE40) + parent coating IPA-ST-UP nanoparticles conc. (PE5) 25PC Film + CN991 Surface, 7.5% 4/4 formed 4/4 molded fine coating(PE40) + parent coating IPA-ST-L nanoparticles conc. (PE3) CE25 PCFilm + Eb 4513 Surface, 15% 2/2 cracked N/A coating (PE39) + parentcoating IPA-ST-UP nanoparticles conc. (PE13) CE26 PC Film + Eb4513Surface, 15% 2/2 hazed N/A coating (PE39) + parent coating IPA-ST-Lnanoparticles conc. (PE9) CE27 PC Film + CN991 Surface, 15% 2/2 crackedN/A coating (PE40) + parent coating IPA-ST-UP nanoparticles conc. (PE13)CE28 PC Film + CN991 Surface, 15% 2/2 hazed N/A coating (PE40) + parentcoating IPA-ST-L nanoparticles conc. (PE9) CE29 PC Film + Eb4513 Bulk,2% in 2/2 formed 1/2 cracked coating + NANOBYK coating 3605 particles(PE41) CE30 PC Film + Eb4513 Bulk, 5% in 4/6 cracked 1/2 crackedcoating + NANOBYK coating 3605 particles (PE43) CE31 PC Film + Eb4513Bulk, 10% in 3/4 cracked 1/1 molded fine coating + NANOBYK coating 3605particles (PE45) CE32 PC Film + CN991 Bulk, 2% in 2/2 formed 2/2 moldedfine coating + NANOBYK coating (1 fouled by old 3605 particles (PE42)resin) CE33 PC Film + CN991 Bulk, 5% in 1/6 cracked 1/5 crackedcoating + NANOBYK coating 3605 particles (PE44) CE34 PC Film + CN991Bulk, 10% in 4/4 formed 2/4 cracked coating + NANOBYK coating 3605particles (PE46)

The initial transmission and haze of Examples 22-25, CE22-24, andCE29-34 were measured with a BYK HAZE GARD I instrument (BYKInstruments, Geretsried, Germany). Results are shown in Table 18. TheExamples were tested for abrasion resistance according to MIL-PRF-32432.Specimen(s) for each condition were tested and the results averaged(where applicable). Abrasive eraser insert per MIL-E-12397B, 20 cycles,1.1 kilogram load, 40 cycles/min. The post-abrasion (final) haze andtransmission were measured on the same instrument. Results are shown inTable 18.

TABLE 18 Hardcoat Testing Post- Post- Example Number Initial InitialAbrasion Abrasion Delta Delta Number Replicates % Transmission % Haze %Transmission % Haze % Transmission % Haze CE22 5 92.3 1.25 87.7 44.7−4.6 43.5 CE23 3 93.1 0.84 89.3 16.1 −3.8 15.3 CE24 4 93.1 0.92 89.416.9 −3.7 16.0 22 3 93.3 1.35 91.9 7.88 −1.4 6.53 23 2 93.5 1.15 90.97.22 −2.6 6.07 24 4 93.4 0.95 91.8 9.10 −1.6 8.15 25 4 93.3 2.40 90.810.1 −2.5 7.70 CE29 1 93.0 1.31 88.8 17.8 −4.2 16.5 CE30 1 92.5 1.1788.9 16.2 −3.6 15.0 CE31 1 91.7 2.12 87.1 22.9 −4.6 20.8 CE32 1 92.81.29 88.5 18.4 −4.3 17.1 CE33 4 92.8 1.02 88.9 18.0 −3.9 17.0 CE34 292.3 1.27 88.3 18.1 −4.0 16.8

Examples 26-30 190 nm Size, Surface-Treated Silica Nanoparticles Coatedonto Donor Polymeric Film at Different Dispersion Concentrations

TABLE 19 Composition of Preparatory Examples 39-43 for Examples 26-30Preparatory Nanoparticle Diluting Final Wt. Example Size, nm Solvent %SiO₂ PE39 190 PGME 0.5 PE40 190 PGME 1.5 PE41 190 PGME 3.0 PE42 190 PGME5.0 PE43 190 PGME 7.5

Nanoparticle dispersions were prepared by diluting 190 nm surfacetreated nano-silica particles with 1-methoxy-2-propanol, according toTable 19. The nanoparticle dispersions were mixed with high agitation ona vortex mixer. PP3, used as received, was cut into an 8 in×12 in (20cm×30.5 cm) sheet. The PP3 sheet was placed upon a flat glass surface.Each nanoparticle dispersion, PE39-43, from Table 19 above, was coatedonto a separate sheet of PP3 with Mayer rod #6 (R D Specialties,Webster, N.Y.). Each of the Mayer rod coatings was approximately 7 in×10in (18 cm×25 cm). All coatings were allowed to air dry for 2-24 hours atroom temperature. Once dried, the nanoparticle coatings were trimmed toapproximately 6 in×10 in (15 cm×25 cm). Additionally, one sheet of PP3without any coating was similarly trimmed. Each of the nanoparticlecoatings and the blank PP3 was placed upon a flat glass surface with thenanoparticle side up (where applicable). A 6 in×9 in (15 cm×23 cm) pieceof PET1 film was gently laid upon the dried nanoparticle coating withthe primed side of PET1 against the nanoparticle coating. In the case ofCE35, the primed side of PET1 was against the uncoated PP3. PET1 wascarefully rolled back from the nanoparticle coating (where applicable)and over Mayer rod #6. A 0.5 mL bead of PE1 was deposited onto thenanoparticle coating with a disposable pipette. The Mayer rod was movedacross the surface of the nanoparticle coating to effect the spreadingof PE1 while simultaneously laminating PET1 to the nanoparticle coating.This technique, wherein the Mayer rod never directly touches the coatingformula, PE1, eliminates air from becoming entrained in the laminate. Inthe case of CE35, the coating formula, PE1, is spread between PET1 andan uncoated sheet of PP3. The laminates were placed under a mediumpressure mercury D bulb radiation source, with the PET1 film being thetopmost layer. The UV processor with the medium pressure mercury D bulbradiation source was a HERAEUS FUSION UV SYSTEMS INC. unit equipped witha LIGHT HAMMER 6 Model LH6 500 W/in (200 W/cm) power source with theoutput power set to 100%. The laminates were carried through the UVprocessor by a conveyor belt system at a speed of 40 feet/minute (12.2m/minute). The PET1 film and the cured coating with capturednanoparticles (where applicable) were peeled as a unit from the surfaceof the PP3.

TABLE 20 Hardcoat Testing, Rotary Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE35 None N/A 92.2 0.41 91.24.06 −1.0 3.65 26 190 nm (PE39) 0.5% 92.2 0.41 91.0 4.48 −1.2 4.07 27190 nm (PE40) 1.5% 92.2 0.42 90.9 3.98 −1.3 3.56 28 190 nm (PE41) 3.0%92.2 0.41 91.1 5.13 −1.1 4.72 29 190 nm (PE42) 5.0% 92.2 0.41 91.4 9.36−0.8 8.95 30 190 nm (PE43) 7.5% 92.3 0.39 91.4 13.4 −0.9 13.0

The initial transmission and haze of Examples 26-30 and CE35 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown Table 20. The examples were tested forabrasion resistance according to ASTM D1044-13. Two specimens for eachcondition were tested and the results averaged. CS-10F abrasive wheels,100 cycles, 500 gram load, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument.

TABLE 21 Hardcoat Testing, Linear Taber Abrasion Nano- particleConcentration Average Average Average Average Delta Nano-particle inTransfer Initial Initial Final Final Delta Haze Example Layer LayerTransmission Haze Transmission Haze Transmission (%) CE35 None N/A 92.20.41 91.3 12.2 −0.9 11.8 26 190 nm (PE39) 0.5% 92.2 0.41 91.5 12.5 −0.712.1 27 190 nm (PE40) 1.5% 92.2 0.42 91.7 9.36 −0.5 8.94 28 190 nm(PE41) 3.0% 92.2 0.41 92.0 6.34 −0.2 5.93 29 190 nm (PE42) 5.0% 92.20.41 91.9 6.37 −0.3 5.96 30 190 nm (PE43) 7.5% 92.3 0.39 92.2 6.52 −0.16.13

The initial transmission and haze of Examples 26-30 and CE35 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown Table 21. The Examples were tested forabrasion resistance according to ASTM D6279-15. Two specimens for eachcondition were tested and the results averaged. SCOTCH-BRITE 07448abrasive pad (available from 3M), 40 cycles, 750 gram load, 3 in (7.6cm) stroke length, cycles/min. The post-abrasion (final) haze andtransmission were measured on the same instrument. The results are shownTable 21.

Examples 31-35 100 nm Size, Surface-Treated Nanoparticles Coated ontoDonor Polymeric Film at Different Dispersion Concentrations

TABLE 22 Composition of Preparatory Examples 44-48 for Examples 31-35Preparatory Nanoparticle Diluting Final Wt. Example Size, nm Solvent %SiO2 PE44 100 PGME 0.5 PE45 100 PGME 1.5 PE46 100 PGME 3.0 PE47 100 PGME5.0 PE48 100 PGME 7.5

Nanoparticle dispersions were prepared by diluting 100 nm surfacetreated nano-silica particles with 1-methoxy-2-propanol, according toTable 22. The nanoparticle dispersions were mixed with high agitation ona vortex mixer. PP3, used as received, was cut into an 8 in×12 in (20cm×30.5 cm) sheet. The PP3 sheet was placed upon a flat glass surface.Each nanoparticle dispersion, PE44-48, from Table 22 above, was coatedonto a separate sheet of PP3 with Mayer rod #6 (R D Specialties,Webster, N.Y.). Each of the Mayer rod coatings was approximately 7 in×10in (18 cm×25 cm). All coatings were allowed to air dry for 2-24 hours atroom temperature. Once dried, the nanoparticle coatings were trimmed toapproximately 6 in×10 in (15 cm×25 cm). Additionally, one sheet of PP3without any coating was similarly trimmed. Each of the nanoparticlecoatings and the blank PP3 was placed upon a flat glass surface with thenanoparticle side up (where applicable). A 6 in×9 in (15 cm×23 cm) pieceof PET1 film was gently laid upon the dried nanoparticle coating withthe primed side of PET1 against the nanoparticle coating. In the case ofCE36, the primed side of PET1 was against the uncoated PP3. PET1 wascarefully rolled back from the nanoparticle coating (where applicable)and over Mayer rod #6. A 0.5 mL bead of PE1 was deposited onto thenanoparticle coating with a disposable pipette. The Mayer rod was movedacross the surface of the nanoparticle coating in order to effect thespreading of PE1 while simultaneously laminating PET1 to thenanoparticle coating. This technique, wherein the Mayer rod neverdirectly touches the coating formula, PE1, eliminates air from becomingentrained in the laminate. In the case of CE36, the coating formula,PE1, is spread between PET1 and an uncoated sheet of PP3. The laminateswere placed under a medium pressure mercury D bulb radiation source,with the PET1 film being the topmost layer. The UV processor with themedium pressure mercury D bulb radiation source was a HERAEUS FUSION UVSYSTEMS INC. unit equipped with a LIGHT HAMMER 6 Model LH6 500 W/in (200W/cm) power source with the output power set to 100%. The laminates werecarried through the UV processor by a conveyor belt system at a speed of40 feet/minute (12.2 m/minute). The PET1 film and the cured coating withcaptured nanoparticles (where applicable) were peeled as a unit from thesurface of the PP3.

TABLE 23 Hardcoat Testing, Rotary Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE36 None N/A 92.2 0.42 91.04.49 −1.2 4.07 31 100 nm (PE44) 0.5% 92.4 0.45 91.1 4.04 −1.3 3.59 32100 nm (PE45) 1.5% 92.7 0.41 91.4 4.34 −1.3 3.93 33 100 nm (PE46) 3.0%92.4 0.42 91.2 7.21 −1.2 6.79 34 100 nm (PE47) 5.0% 92.3 0.39 91.4 9.11−0.9 8.72 35 100 nm (PE48) 7.5% 92.4 0.41 91.4 11.3 −1.0 10.9

The initial transmission and haze of Examples 31-35 and CE36 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in Table 23. The Examples were testedfor abrasion resistance according to ASTM D1044-13. Two specimens foreach condition were tested and the results averaged. CS-10F abrasivewheels, 100 cycles, 500 gram load, 60 cycles/min. The post-abrasion(final) haze and transmission were measured on the same instrument.

TABLE 24 Hardcoat Testing, Linear Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer

Transmission Haze Transmission Haze Transmission Haze CE36 None N/A 92.20.42 91.0 15.2 −1.2 14.8 31 100 nm

0.5% 92.4 0.45 92.0 8.48 −0.4 8.03 32 100 nm

1.5% 92.7 0.41 92.4 5.89 −0.3 5.48 33 100 nm (PE46) 3.0% 92.4 0.42 92.45.09 0.0 4.67 34 100 nm

5.0% 92.3 0.39 92.5 4.96 0.2 4.57 35 100 nm

7.5% 92.4 0.41 92.4 6.98 0.0 6.57

indicates data missing or illegible when filed

The initial transmission and haze of Examples 31-35 and CE36 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D6279-15. Two specimensfor each condition were tested and the results averaged. SCOTCH-BRITE07448 abrasive pad (available from 3M), 40 cycles, 750 gram load, 3 in(7.6 cm) stroke length, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument.

Examples 36-40 75 nm Size, Surface-Treated Nanoparticles Coated ontoDonor Polymeric Film at Different Dispersion Concentrations

TABLE 25 Composition of Preparatory Examples 49-53 for Examples 36-40Preparatory Nanoparticle Diluting Final Wt. Example Size, nm Solvent %SiO2 PE49 75 PGME 0.5 PE50 75 PGME 1.5 PE51 75 PGME 3.0 PE52 75 PGME 5.0PE53 75 PGME 7.5

Nanoparticle dispersions were prepared by diluting 75 nm surface treatednano-silica particles with 1-methoxy-2-propanol, according to Table 25.The nanoparticle dispersions were mixed with high agitation on a vortexmixer. PP3, used as received, was cut into an 8 in×12 in (20 cm×30.5 cm)sheet. The PP3 sheet was placed upon a flat glass surface. Eachnanoparticle dispersion, PE49-53, from Table 25 above, was coated onto aseparate sheet of PP3 with Mayer rod #6 (R D Specialties, Webster,N.Y.). Each of the Mayer rod coatings was approximately 7 in×10 in (18cm×25 cm). All coatings were allowed to air dry for 2-24 hours at roomtemperature. Once dried, the nanoparticle coatings were trimmed toapproximately 6 in×in (15 cm×25 cm). Additionally, one sheet of PP3without any coating was similarly trimmed. Each of the nanoparticlecoatings and the blank PP3 was placed upon a flat glass surface with thenanoparticle side up (where applicable). A 6 in×9 in (15 cm×23 cm) pieceof PET1 film was gently laid upon the dried nanoparticle coating withthe primed side of PET1 against the nanoparticle coating. In the case ofCE37, the primed side of PET1 was against the uncoated PP3. PET1 wascarefully rolled back from the nanoparticle coating (where applicable)and over Mayer rod #6. A 0.5 mL bead of PE1 was deposited onto thenanoparticle coating with a disposable pipette. The Mayer rod was movedacross the surface of the nanoparticle coating in order to effect thespreading of PE1 while simultaneously laminating PET1 to thenanoparticle coating. This technique, wherein the Mayer rod neverdirectly touches the coating formula, PE1, eliminates air from becomingentrained in the laminate. In the case of CE37, the coating formula,PE1, is spread between PET1 and an uncoated sheet of PP3. The laminateswere placed under a medium pressure mercury D bulb radiation source,with the PET1 film being the topmost layer. The UV processor with themedium pressure mercury D bulb radiation source was a HERAEUS FUSION UVSYSTEMS INC. unit equipped with a LIGHT HAMMER 6 Model LH6 500 W/in (200W/cm) power source with the output power set to 100%. The laminates werecarried through the UV processor by a conveyor belt system at a speed of40 feet/minute (12.2 m/minute). The PET1 film and the cured coating withcaptured nanoparticles (where applicable) were peeled as a unit from thesurface of the PP3.

TABLE 26 Hardcoat Testing, Rotary Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE37 None N/A 92.1 0.40 91.34.05 −0.8 3.65 36 75 nm (PE49) 0.5% 92.4 0.40 91.4 4.96 −1.0 4.56 37 75nm (PE50) 1.5% 92.5 0.39 91.5 3.81 −1.0 3.42 38 75 nm (PE51) 3.0% 92.30.38 91.6 6.19 −0.7 5.81 39 75 nm (PE52) 5.0% 92.3 0.39 91.5 7.02 −0.86.63 40 75 nm (PE53) 7.5% 92.4 0.36 91.6 7.06 −0.8 6.70

The initial transmission and haze of Examples 36-40 and CE37 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D1044-13. Two specimensfor each condition were tested and the results averaged. CS-10F abrasivewheels, 100 cycles, 500 gram load, 60 cycles/min. The post-abrasion(final) haze and transmission were measured on the same instrument.

TABLE 27 Hardcoat Testing, Linear Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE37 None N/A 92.1 0.40 91.215.2 −0.9 14.8 36 75 nm (PE49) 0.5% 92.4 0.40 92.0 9.64 −0.4 9.24 37 75nm (PE50) 1.5% 92.5 0.39 92.6 5.62 0.1 5.23 38 75 nm (PE51) 3.0% 92.30.38 92.5 6.39 0.2 6.01 39 75 nm (PE52) 5.0% 92.3 0.39 92.6 6.02 0.35.63 40 75 nm (PE53) 7.5% 92.4 0.36 92.6 6.81 0.2 6.45

The initial transmission and haze of Examples 36-40 and CE37 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D6279-15. Two specimensfor each condition were tested and the results averaged. SCOTCH-BRITE07448 abrasive pad (available from 3M), 40 cycles, 750 gram load, 3 in(7.6 cm) stroke length, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument.

Examples 41-45 20 nm Size, Surface-Treated Nanoparticles Coated ontoDonor Polymeric Film at Different Dispersion Concentrations

TABLE 28 Composition of Preparatory Examples 54-58 for Examples 41-45Preparatory Nanoparticle Diluting Final Wt. Example Size, nm Solvent %SiO₂ PE54 20 PGME 0.5 PE55 20 PGME 1.5 PE56 20 PGME 3.0 PE57 20 PGME 5.0PE58 20 PGME 7.5

Nanoparticle dispersions were prepared by diluting 20 nm surface treatednano-silica particles with 1-methoxy-2-propanol, according to Table 28.The nanoparticle dispersions were mixed with high agitation on a vortexmixer. PP3, used as received, was cut into an 8 in×12 in (20 cm×30.5 cm)sheet. The PP3 sheet was placed upon a flat glass surface. Eachnanoparticle dispersion, PE54-58, from Table 28 above, was coated onto aseparate sheet of PP3 with Mayer rod #6 (R D Specialties, Webster,N.Y.). Each of the Mayer rod coatings was approximately 7 in×10 in (18cm×25 cm). All coatings were allowed to air dry for 2-24 hours at roomtemperature. Once dried, the nanoparticle coatings were trimmed toapproximately 6 in×10 in (15 cm×25 cm). Additionally, one sheet of PP3without any coating was similarly trimmed. Each of the nanoparticlecoatings and the blank PP3 was placed upon a flat glass surface with thenanoparticle side up (where applicable). A 6 in×9 in (15 cm×23 cm) pieceof PET1 film was gently laid upon the dried nanoparticle coating withthe primed side of PET1 against the nanoparticle coating. In the case ofCE38, the primed side of PET1 was against the uncoated PP3. PET1 wascarefully rolled back from the nanoparticle coating (where applicable)and over Mayer rod #6. A 0.5 mL bead of PE1 was deposited onto thenanoparticle coating with a disposable pipette. The Mayer rod was movedacross the surface of the nanoparticle coating in order to effect thespreading of PE1 while simultaneously laminating PET1 to thenanoparticle coating. This technique, wherein the Mayer rod neverdirectly touches the coating formula, PE1, eliminates air from becomingentrained in the laminate. In the case of CE38, the coating formula,PE1, is spread between PET1 and an uncoated sheet of PP3. The laminateswere placed under a medium pressure mercury D bulb radiation source,with the PET1 film being the topmost layer. The UV processor with themedium pressure mercury D bulb radiation source was a HERAEUS FUSION UVSYSTEMS INC. unit equipped with a LIGHT HAMMER 6 Model LH6 500 W/in (200W/cm) power source with the output power set to 100%. The laminates werecarried through the UV processor by a conveyor belt system at a speed of40 feet/minute (12.2 m/minute). The PET1 film and the cured coating withcaptured nanoparticles (where applicable) were peeled as a unit from thesurface of the PP3.

TABLE 29 Hardcoat Testing, Rotary Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE38 None N/A 92.1 0.42 91.03.77 −1.1 3.35 41 20 nm (PE54) 0.5% 92.3 0.41 91.0 4.31 −1.3 3.90 42 20nm (PE55) 1.5% 92.5 0.43 91.4 3.50 −1.1 3.07 43 20 nm (PE56) 3.0% 92.30.42 91.1 5.14 −1.2 4.72 44 20 nm (PE57) 5.0% 92.3 0.42 91.0 6.62 −1.36.20 45 20 nm (PE58) 7.5% 92.3 0.41 91.2 7.67 −1.1 7.26

The initial transmission and haze of Examples 41-45 and CE38 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D1044-13. Two specimensfor each condition were tested and the results averaged. CS-10F abrasivewheels, 100 cycles, 500 gram load, 60 cycles/min. The post-abrasion(final) haze and transmission were measured on the same instrument.

TABLE 30 Hardcoat Testing, Linear Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE38 None N/A 92.1 0.42 90.717.2 −1.4 16.8 41 20 nm (PE54) 0.5% 92.3 0.41 91.0 15.70 −1.3 15.3 42 20nm (PE55) 1.5% 92.5 0.43 91.8 9.37 −0.7 8.94 43 20 nm (PE56) 3.0% 92.30.42 92.1 5.95 −0.2 5.53 44 20 nm (PE57) 5.0% 92.3 0.42 92.2 5.77 −0.15.35 45 20 nm (PE58) 7.5% 92.3 0.41 92.3 4.81 0.0 4.40

The initial transmission and haze of Examples 41-45 and CE38 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D6279-15. Two specimensfor each condition were tested and the results averaged. SCOTCH-BRITE07448 abrasive pad (available from 3M), 40 cycles, 750 gram load, 3 in(7.6 cm) stroke length, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument.

Examples 46-50 5 nm Size, Surface-Treated Nanoparticles Coated ontoDonor Polymeric Film at Different Dispersion Concentrations

TABLE 31 Composition of Preparatory Examples 59-63 for Examples 46-50Preparatory Nanoparticle Diluting Final Wt. Example Size, nm Solvent %SiO2 PE59 5 PGME 0.5 PE60 5 PGME 1.5 PE61 5 PGME 3.0 PE62 5 PGME 5.0PE63 5 PGME 7.5

Nanoparticle dispersions were prepared by diluting 5 nm surface treatednano-silica particles with 1-methoxy-2-propanol, according to Table 31.The nanoparticle dispersions were mixed with high agitation on a vortexmixer. PP3, used as received, was cut into an 8 in×12 in (20 cm×30.5 cm)sheet. The PP3 sheet was placed upon a flat glass surface. Eachnanoparticle dispersion, PE59-63, from Table 31 above, was coated onto aseparate sheet of PP3 with Mayer rod #6 (R D Specialties, Webster,N.Y.). Each of the Mayer rod coatings was approximately 7 in×10 in (18cm×25 cm). All coatings were allowed to air dry for 2-24 hours at roomtemperature. Once dried, the nanoparticle coatings were trimmed toapproximately 6 in×10 in (15 cm×25 cm). Additionally, one sheet of PP3without any coating was similarly trimmed. Each of the nanoparticlecoatings and the blank PP3 was placed upon a flat glass surface with thenanoparticle side up (where applicable). A 6 in×9 in (15 cm×23 cm) pieceof PET1 film was gently laid upon the dried nanoparticle coating withthe primed side of PET1 against the nanoparticle coating. In the case ofCE39, the primed side of PET1 was against the uncoated PP3. PET1 wascarefully rolled back from the nanoparticle coating (where applicable)and over Mayer rod #6. A 0.5 mL bead of PE1 was deposited onto thenanoparticle coating with a disposable pipette. The Mayer rod was movedacross the surface of the nanoparticle coating in order to effect thespreading of PE1 while simultaneously laminating PET1 to thenanoparticle coating. This technique, wherein the Mayer rod neverdirectly touches the coating formula, PE1, eliminates air from becomingentrained in the laminate. In the case of CE39, the coating formula,PE1, is spread between PET1 and an uncoated sheet of PP3. The laminateswere placed under a medium pressure mercury D bulb radiation source,with the PET1 film being the topmost layer. The UV processor with themedium pressure mercury D bulb radiation source was a HERAEUS FUSION UVSYSTEMS INC. unit equipped with a LIGHT HAMMER 6 Model LH6 500 W/in (200W/cm) power source with the output power set to 100%. The laminates werecarried through the UV processor by a conveyor belt system at a speed of40 feet/minute (12.2 m/minute). The PET1 film and the cured coating withcaptured nanoparticles (where applicable) were peeled as a unit from thesurface of the PP3.

TABLE 32 Hardcoat Testing, Rotary Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE39 None N/A 92.2 0.45 91.13.68 −1.1 3.23 46 5 nm (PE59) 0.5% 92.4 0.43 91.2 3.86 −1.2 3.43 47 5 nm(PE60) 1.5% 92.6 0.42 91.4 3.45 −1.2 3.03 48 5 nm (PE61) 3.0% 92.4 0.4091.3 2.43 −1.1 2.03 49 5 nm (PE62) 5.0% 92.3 0.42 91.3 2.52 −1.0 2.10 505 nm (PE63) 7.5% 92.3 0.42 91.4 2.34 −0.9 1.92

The initial transmission and haze of Examples 46-50 and CE39 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D1044-13. Two specimensfor each condition were tested and the results averaged. CS-10F abrasivewheels, 100 cycles, 500 gram load, 60 cycles/min. The post-abrasion(final) haze and transmission were measured on the same instrument.

TABLE 33 Hardcoat Testing, Linear Taber Abrasion Nano- particleConcentration Average Average Average Average Nano-particle in TransferInitial Initial Final Final Delta Delta Example Layer Layer TransmissionHaze Transmission Haze Transmission Haze CE39 None N/A 92.2 0.45 90.915.4 −1.3 15.0 46 5 nm (PE59) 0.5% 92.4 0.43 90.7 17.2 −1.7 16.8 47 5 nm(PE60) 1.5% 92.6 0.42 90.9 14.5 −1.7 14.1 48 5 nm (PE61) 3.0% 92.4 0.4091.8 7.32 −0.6 6.92 49 5 nm (PE62) 5.0% 92.3 0.42 91.8 5.02 −0.5 4.60 505 nm (PE63) 7.5% 92.3 0.42 92.2 2.60 −0.1 2.18

The initial transmission and haze of Examples 46-50 and CE39 weremeasured with a BYK HAZE GARD I instrument (BYK Instruments, Geretsried,Germany). The results are shown in the table above. The examples weretested for abrasion resistance according to ASTM D6279-15. Two specimensfor each condition were tested and the results averaged. SCOTCH-BRITE07448 abrasive pad (available from 3M), 40 cycles, 750 gram load, 3 in(7.6 cm) stroke length, 60 cycles/min. The post-abrasion (final) hazeand transmission were measured on the same instrument.

All cited references, patents, and patent applications in the aboveapplication for letters patent are herein incorporated by reference intheir entirety in a consistent manner. In the event of inconsistenciesor contradictions between portions of the incorporated references andthis application, the information in the preceding description shallcontrol. The preceding description, given in order to enable one ofordinary skill in the art to practice the claimed disclosure, is not tobe construed as limiting the scope of the present disclosure.

1. A coating composition comprising: a nanoparticle layer comprisingnanoparticles and a curable resin; and a curable resin layer comprisingthe curable resin, wherein the nanoparticle layer has a thickness of 0.2μm to 8 μm, and wherein the nanoparticle layer comprises less than 40vol. % of the curable resin.
 2. The coating composition of claim 1,wherein the nanoparticle layer has a thickness of 0.4 μm to 6 μm,optionally 0.8 μm to 4 μm, or optionally 1 μm to 3 μm.
 3. The coatingcomposition of claim 1, wherein the nanoparticle layer comprises lessthan 30 vol. %, less than 20 vol. %, less than 10 vol. %, less than 5vol. %, or less than 1 vol. % of the curable resin.
 4. The coatingcomposition of claim 1, wherein the nanoparticles comprise silica,alumina, ceria, diamond, titanium dioxide, zinc oxide, tungsten oxide,zirconia, calcium carbonate, magnesium silicate, indium tin oxide,antimony tin oxide, tungsten bronze, and combinations thereof.
 5. Thecoating composition of claim 4, wherein the nanoparticles have averagediameters of from 1 nm to 400 nm, optionally 2 nm to 200 nm, oroptionally 5 nm to 100 nm.
 6. The coating composition of claim 1,wherein the nanoparticles have an aspect ratio of 2:1 to 12:1,optionally 3:1 to 11:1, optionally 4:1 to 10:1, optionally 5:1 to 9:1.7. The coating composition of claim 1, wherein the nanoparticlescomprise an elongated silica nanoparticle having a diameter of 9 nm to15 nm and a length of 40 nm to 100 nm.
 8. The coating composition ofclaim 1, wherein the nanoparticles comprise a silane coating.
 9. Thecoating composition of claim 1, wherein the curable resin comprises a(meth)acrylate resin, a polyurethane precursor, an epoxy precursor, apolyurea precursor, a cyanoacrylate resin, a polyester (meth)acrylateresin, a polyurethane (meth)acrylate resin, and combinations thereof.10. The coating composition of claim 1, wherein the curable resincomprises a (meth)acrylate resin.
 11. The coating composition of claim10, wherein the (meth)acrylate resin comprises at least one(meth)acrylate component having a functionality of two or higher. 12.The coating composition of claim 1, wherein the curable resin furthercomprises wt. % to 60 wt. %, 0.1 wt. % to 20 wt. %, or 0.1 wt. % to 10wt of a nanoparticle dispersed throughout the curable resin bulk. 13.The coating composition of claim 1, wherein the curable resin is free ofdispersed nanoparticles.
 14. The coating composition of claim 1, whereinthe curable resin further comprises 0.1 wt. % to 10 wt. % of aphotoinitiator.
 15. The coating composition of claim 1, wherein thecurable resin further comprises an additive selected from the groupconsisting of a pigment, an antioxidant, a surfactant, a solvent, awetting aid, a slip agent, a leveling agent, and combinations thereof.16. A hardcoat prepared using the coating composition of claim
 1. 17.The hardcoat of claim 13, wherein the hardcoat has a delta haze % lessthan 25, less than 10, less than 5, less than 2.5, or less than 2according to ASTM D1044-13.
 18. A laminate comprising: the coatingcomposition of claim 1; and a substrate, wherein the substrate isadjacent the curable resin layer. 19-22. (canceled)
 23. A method ofcoating a substrate, the method comprising: preparing the coatingcomposition of claim 1; and applying the coating composition to asubstrate wherein the substrate is adjacent the curable resin layer. 24.The method of claim 23, further comprising exposing the substrate toactinic radiation.